Phenylthionocarbamates



United States Patent No Drawing. Filed Apr. 2, 1962, Ser. No. 184,486 '15 Claims. (Cl. 260-2471) This application is a continuation-in-part of now abandoned copending applications Serial No. 736,968, filed May 22, 1958, Serial No. 843,646, filed October 1, 1959, Serial No. 843,948, filed October 2, 1959 and Serial No. 844,195, filed October 5, 1959.

The present invention relates to phenylthionocarbamates, to biologically active compositions containing them as an essential active ingredient and to methods of using such biologically active compositions. More particularly, the invention relates to phenylthionocarbamates which contain in the phenyl radical substituents which support biological activity. The biological activity is further supported by a heterocyclic radical containing the nitrogen of the thionocarbamic acid radical.

General objects of the invention are to provide useful new compounds, especially compounds which are toxic to living plants and to provide methods fortheir use to accomplish various desirable results. A further object is to provide compositions and methods for the destruction of noxious vegetation. Another object is to destroy weeds in the form of germinating seedlings. Another object is to destroy weeds by applying a toxic concentration of the new compounds to foliage after emergence. Still another object is to provide new compounds which are outstandingly elfective herbicides and to provide methods for manufacture of such compounds. A particular object of the invention is to provide herbicides characterized by high unit activity and specificity for the control of weeds in the most prevalent broadleaf weed families and weedy grass families. A further object is to provide new fungicides.

An important segment of the new compounds are the mono-, diand trihalogenated phenyl esters which may be represented by the general formula where X represents halogen, preferably chlorine, n represents an integer from 1 to 3 inclusive and R is a heterocyclic amino radical nitrogen of. which is attached to the thiocarbonyl group. The presence of halogen in the phenyl radical is essential for obtaining the desired properties and, in general, so is the heterocyclic amino radical. Tetraand pentahalogen substituted phenyl esters are less desirable.

In addition to halogen, a lower alkyl group in the phenyl ring is permitted. Phenyl radicals so substituted include p-chloro-o-tolyl, o-chloro-p-tolyl and 2-bromo-4-butylphenyl. The butyl radical may be primary, secondary or tertiary and bromine may be replaced by chlorine. In other words, the halogen may be a middle halogen. In the case of dihalophenyl radicals 2,4-orientation is preferred but R should not contain oxygen unless the halo- "ice gens are chlorine. In the monohalophenyl series it was demonstrated that the halogen could be chlorine, bromine or fluorine but could not be p-bromophenyl when R'was dirnethylmorpholino. The terms morpholino and piperidino refer only to radicals having the free valence on the nitrogen in accordance with accepted usage and in the interest of uniformity the terms pyrrolidino, N- methylpiperazino and hexamethylenimino will be employed herein to designate that substitution is in the 1- position.

The invention will be more readily understood from typical examples of the preferred compounds which comprise o-, mand p-chlorophenyl, 0-, mand p-bromophenyl, 0-, mand p-fluorophenyl, 2,4-dichlorophenyl, 2,4 di fluorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl and 2,3- dichlorophenyl esters of 4-morpholinecarbothionic acid; 2,3,4-trichlorophenyl, 2,3,4-tribromophenyl, 2,3,5-trichlorophenyl, 2,3,5-tribromophenyl, 2,4,5-tribromophenyl, 2,4,5 trifluorophenyl, 2,3,6 trichlorophenyl, 2,3, 6 tribromophenyl, 2,4,6 trichlorophenyl, 2,4,6 tribromophenyl and 2,4,6 trifluorophenyl esters of l pyrrolidinecarbothionic acid. Further examples are the pchlorophenyl esters of the following:

Although other methods of syntheses are applicable the new compounds are probably most readily obtained by condensing a halogen substituted phenol with an aminocarbonyl halide containing the desired acid radical. The detailed examples below fully describe this phase of the invention but the invention is not limited thereto.

EXAMPLE 1 A solution was prepared by admixing 32.1 grams (0.25 mole) of p-chlorophenol, 150 ml. of benzene and 30 ml. of triethylarnine. To the solution so prepared was added slowly 41.4 grams (0.25 mole) of 4-morpholinethiocarbonyl chloride. The exothermic reaction caused a temperature rise from 27 to 35 C. The reaction mixture was refluxed overnight, cooled and diluted with 250 ml. of water. The solution was extracted with 250 ml. of ether, the ether extract washed with water three times and dried over sodium sulfate. The product was filtered through clay and the solvent removed by distillation in vacuo at C. (approximately 14 mm. Hg). The residue, 58 grams of a semi-solid, was added to 50 ml. of ethanol and the mixture heated. The portion insoluble in ethanol was separated by filtering the hot mixture. The p-chlorophenylArmorpholinecarbothionate was recovered from thefiltrate as a pale yellow solid melting at 103-106 C. Analysis gave 5.7% nitrogen, 12.8% sulfur and 13.8% chlorine as compared to 5.4% nitrogen, 12.4% sulfur and 13.8% chlorine calculated for C H CINO S.

EXAMPLE 2 4 EXAMPLE 7 To a stirred solution containing 32.1 grams (0.25 mole) of p-chlorophenol and 40 grams (0.25 mole) of 25% I th procedure f E l 1 4( 7 grams 02,5 mole) 5 sodium hydroxide was added in one portion at room temof 2,4-dichlorophenol was substituted for the p-chloro- Peratufe grams mole) of l phenol, Th 2,4 di h1 h 1 4- h 1i b hi pholinethiocarbonyl chloride in 50 ml. of acetone. The nate was a pale yellow solid melting at 86-88 C. Analytemperature rose to and was p thel'e by sis gave 4.7% nitrogen as compared to 4.8% calculated eeeling- When the temperature started to p the ice for C H CI NO S 10 bath was removed, the product stirred for 5 hours at room EXAMPLE 3 temperature and then 250 ml. of water added. The solution was filtered and the solid Washed with water and A solution was prepared by admixing 43.2 grams (0.25 dried on a porous plate. The p-chlorophenyl 4-(2,6- 111016) of P- p 150 ml. of benzene and 30 ml. dimethyl)morpholinecarbothionate was obtained in 56% of triethylamine. To the cooled solution so prepared yield as a tan solid melting at 117-118 C. after recrys was added Slowly grams mole) of mofpholilletallization from ethanol/water. Analysis gave 12.5% thiocarbonyl chloride and the mixture refluxed overnight. chlorine, 11.4% sulfur and 5.0% nitrogen as compared to h Preduee Was Washed With 2 N NHOH and then d l 12.4% chlorine, 11.2% sulfur and 4.9% nitrogen calwith-150 ml. of water. The solution was extracted with culated,

250 ml. of ether and the organic layer washed with water EXAMPLE 3 and dried over sodium sulfate. The product was filtered i through clay and the solvent removed by distillation in To astlfred Solutlefl eentelnlng grams mole) vacu-o at 100 C. After recrystallizing from ethanol the of P'fluefephenel grams mole) of 25% p-bromophenyl 4-moropholinecarbothionate was an amber Sodlum hydroxide was added in one P at a solid melting at 97-100 C. Analysis gave 10.2% sulfur Solution of grams (0115 mole) of 83% 4-II10I'Ph01iI1ed 49% nitrogen as compared to 105% ulf and 25 thiocarbonyl chloride in 80 ml. of acetone. The tem- 4,7% nitrogen l l d f H B O S perature was allowed to rise to C. 'but was kept from XAMPLE 4 rising higher by cooling in an ice bath. After cooling to E room temperature the mixture was stirred for 5 hours at To a stirred solution containing 32.4 grams (0.25 mole) room temperature, 250 ml. of water then added, the solid of o-chlorop-henol and 40 grams (0.25 mole) of 25% 30 filtered, washed with water and air dried. The p-fiuorosodium hydroxide was added in one portion at 25'30 C. phenyl -4-morpholinecarbothionate was obtained in 77. 2% a solution of46 grams (0.25 mole) of 88% 4-rnorpholineyield as a white solid. It melted at 100-102 C. after thiocarbonyl chloride in 50 ml. of acetone. After stirring recrystallization from ethanol. Analysis gave 13.3% the mixture for 4 hours at room temperature, 250 ml. of sulfur and 5.8% nitrogen as compared to 13.3% sulfur Water were added and the solution extracted with 250 ml. 35 and 5.8% nitrogen calculated. of ether. The ether extract was washed with water and The physical properties of other typical examples dried over sodium sulfate. The solvent was removed prepared in similar manner to Example 8 are summarized in vacuo at a maximum temperature of 100 C. at 14 below:

Table II Analysis, percent Example Compound Physical N0. Appearance Calcd. Found 9 2,4-dibromophenyl l-pyr- Tan solid 43. 8 43. 4 rolidinecarbothionate. l LP. 79-81I 8.8 9. 0 10 2,4,5-trichlorophenyl1- Tan solid 34.2 34.4 prrolidinecarbothionate. 16.1. 9l92 10. 3 10.3 11 2,4,6-tricl1lorophenyl 1- Tart sohd 34. 2 84. 4 pyrrolidinecarbothionate. l1V{1:.Cll6 10. 3 10. 3 12 p-Chlorophenyl l-pyrroli- Tan solid 1 14. 7 15.1 dinecarbothionate. l/LP. 75-76 13. 3 12.7

1 Dried on porous plate.

EXAMPLE 13 mm. pressure. The o-chlorophenyl 4-morpholinecarbothionate was obtained as a yellow solid. After recrystallizing from a solution of ethanol and water it melted at 5657 C. Analysis gave 13.8% chlorine, 13.0% sulfur and 5.3% nitrogen as compared to calculated values of 13. 8% chlorine, 12.4% sulfur and 5.5% nitrogen,

The physical properties of other typical examples prepared in similar manner to Example 4 are summarized below:

To a stirred solution containing 34.6 grams (0.2 mole) 60 of p-bromophenol and 32.0 grams (0.2 mole) of 25% The temperature mixture was stirred for 5 hours at room temperature and then 250 ml. of water added. The solution was then extracted with 250 ml. of ether, the ether extract washed with water, dried over sodium sulfate and the solvent stripped at a maximum temperature of 100 C. at 14 mm. pressure. The oil obtained was added to 5 ml. of ethanol and the insoluble portion which separated as a semi-solid was dried on a porous plate. The p-bromophenyl l-pyrrolidinecarbothionate so obtained was a tan solid melting at 65-67 C. after recrystallization from ethanol. Analysis gave 27.9% bromine and 11.0% sulfur as compared to calculated values of 27.9% bromine and 11.12%

sulfur.

EXAMPLE 14 To a stirred solution containing 32.6 grams (0.2 mole) of 2,4-dichlorophenol and 32.0 grams (0.2 mole) of 25% sodium hydroxide was added in one portion at 25 C. a solution of 38.7 grams (0.2 mole) of 4-(2,6-dimethyl)- morpholine thiocarbonyl chloride in 80 ml. of acetone. The temperature rose to 45 C. but Was kept from rising higher by cooling in an ice bath. After cooling to room temperature the mixture was stirred for 5 hours at room temperature and then extracted with 250 ml. of ether. The ether extract was washed with 250 ml. of water, dried over sodium sulfate and the solvent stripped at a maximum temperature of 100 C. at 14 mm. pressure. The oil which separated initially solidified on standing and was dried on a porous plate. The 2,4- dichlorophenyl 4-(2,6-dimethyl)morpholinecarbothionate was a pale yellow solid melting at 82-84 C. after recrystallization from ethanol. Analysis gave 22.1% chlorine, 10.5% sulfur and 4.3% nitrogen as compared to calculated values of 22.1% chlorine, 10.0% sulfur and 4.4% nitrogen.

EXAMPLE 15 In the procedure of Example 14, 29.9 grams (0.2 mole) of l-pyrrolidinethiocarbonyl chloride was substituted for the 4 (2,6 dimethyl)morpholinethiocarbonyl chloride. The 2,4-dichlorophenyl 1-pyrrolidinecarbothionate so obtained was a tan solid melting at 54-56 C. after re- Crystallization from ethanol. Analysis gave 24.3% chlorine, 12.1% sulfur and 4.9% nitrogen as compared to calculated values of 25.7% chlorine, 11.6% sulfur and 5.1% nitrogen.

EXAMPLE 16 To a stirred solution containing 12.9 grams (0.1 mole) of p-chlorophenol, 6.3 grams (0.1 mole) of 90% potassium hydroxide and 200 ml. of acetone was added dropwise at 25-30 C. a solution of l-hexamethylenimincthiocarbonyl chloride in 100 ml. of acetone. The mixture was then stirred at 25-30" C. for 24 hours whereupon 300 ml. of water and 300 ml. of ethyl ether were added and the solution stirred for 15 minutes. The ether solution was washed with water until neutral to litmus and dried over sodium sulfate. The ether was removed in vacuo at a maximum temperature of 80-90 C./12 mm. p-Chlorophenyl 1-hexamethyleniminecarbothionate was obtained in 98.8% yield as a dark amber liquid. Analysis gave 4.7% nitrogen, 11.9% sulfur and 14.1% chlorine compared to 5.2% nitrogen, 11.9% sulfur and 13.1% chlorine calculated for C H ClNOS.

EXAMPLE 17 In the procedure of Example 16, 16.3 grams (0.1 mole) of 2,4-dichlorophenol was substituted for the pchlorophenol. 2,4-dichlorophenyl l-hexamethyleniminecarbothionate was obtained in 95.5% yield as an amber 6 oil. Analysis gave 4.8% nitrogen as compared to 4.6% calculated for C H Cl NOS.

The O-haloaryl aminocarbothionates of this invention are effective in either contact or pro-emergent application. Accordingly, by applying the toxicant to the plant is meant any means whereby the toxicant is brought into contact with living plants which latter include germinating seedlings, as for example by application to the ground before the plants emerge, or by direct application to the foliage. The toxicants may be applied in the form of a spray containing the active ingredient in a concentration within the range of 0.05%-5.0%. Thorough coverage of the foliage is effective for contact killing. For pre-emergent application amounts within the range of 1 to 60 pounds per acre will be adequate for most purposes. The active components are insoluble in water but they are soluble in common organic solvents. They may be dispersed directly in water or dissolved first in an organic solvent and then dispersed. As dispersing and wetting agents there may be employed soft or hard sodium or potassium soaps, alkylated aromatic sodium sulfonates such as sodium dodecylbenzenesulfonate, or an amine salt thereof, alkali metalsalts of sulfated fatty alcohols, ethylene oxide condensation products of alkyl phenols, tall oil, higher alcohols or higher mercaptans. The herbicides may be formulated and applied as dry compositions by mixing the toxicant with a finely divided solid carrier, as for example "talc, pyrophyllite, silica and fullers earth. Formulation of emulsifiable concentrates is feasible to provide compositions convenient for diluting to the concentration desired for application. For this purpose a petroleum base hydrocarbon solvent high in aromatic content is desirable as solvent carrier. A compatible emulsifying agent is added to aid in emulsifying in water.

From the standpoint of activity and weed specificity the new compounds are outstanding. They control two of the most prevalent broadleaf weed families, pigweed and lambs-quarter. They also control three major midwest weedy grasses, crab grass, foxtail and barnyard grass. They are effective on all five plant species at rates down to 1 pound per acre and are effective on some of them at /2 pound per acre. Moreover, they are relatively non toxic to such crops as corn, radish, soybeans, snapbeans and carrots. To the list of weeds controlled may be added smartweed, curl dock, and sheep sorrel, all representatives of another one of the most prevalent weed families (Polygonaceae).

Table III illustrates the pre-emergent herbicidal activity of typical O-haloaryl.aminocarbothionates. The ester was emulsified in Water and the emulsion applied as a spray. In this manner, the active ingredient at a dosage of 5 pounds per acre was applied to the ground of seeded plots before the grass 'or other plants emerged. About fourteen days after application of the toxicants results were observed and recorded. The number of seeds Percent emergence: .Phytotoxicity rating 0-25 3 or severe. 26-50 20rmoderate. 51-75 1 or slight. 76-100 0 or-none.

T able III Active Ingredient Results Observed p-Chlorophenyl 4-morpho1inecarbothionate.

2,4-dicl1lorophenyl d-morphollnecarbothionate.

p-Bromophenyl 4-morpholinecarbothlonate.

2,4-dibromophenyl l-pyrrolidinecarbothlonate.

p-Bromophenyl l-pyrrolidlnecarbothionate.

p-Chlorophenyl l-pyrrolidinecarbothionate.

p-Fluorophenyl 4-morphollnecarbothionate.

2,4-dichlorophenyl l-pyrrolidinecarbothionate.

2,4,5-trlchloropheny1 l-pyrrolidinecarbothionate.

p-Chlorophenyl l-piperidineearbothionate.

Severe phytotoxicity to rye grass, sugar-beet, barnyard grass, crab grass, pigweed and wild buckwheat; moderate phytotoxicity to wild oats, brome grass and tomato.

Severe phytotoxicity to foxtail, barynard grass,

pigweed and crab grass; moderate phytotoxicity to brorne grass.

Severe phytotoxicity to brome grass, rye grass,

sugar-beet, barnyard grass, crab grass, pigweed, tomato and wild buckwheat; moderate phytotoxicity to wild oats.

Severe phytotoxicity to bromc grass, rye grass, barynard grass, crab grass, pigweed and tomato.

Severe phytotoxicity to wild oats, brome grass, rye grass, sugar-beet, barnyard grass, crab grass, pigweed, wild buckwheat and tomato.

Severe phytotoxicity to Wild oats, brome grass,

rye grass, radish (mustard), sugar-beet, barnyard grass, crab grass, pigweed, wild buckwheat, tomato and sorghum.

Severe phytotoxioity to sugar-beet, barnyard grass, crab grass, pigweed, wild buckwheat and tomato; moderate phytotoxicity to sorghum.

Severe phytotoxicity to brome grass, rye grass, sugar-beet, barnyard grass, crab grass, pigweed and sorghum; moderate phytotoxicity to wild oats and tomato.

Severe phytotoxicity to brome grass, barnyard grass, crab grass, pigweed and tomato; moderate phytotoxicity to wild oats and rye grass.

Severe phytotoxicity to rye grass, barnyard grass, crab grass and pigweed; moderate phytotoxicity to wild oats, tomato and sorghum.

When tested at lower concentrations, the above com- 30 pounds completely controlled barnyard grass and pigweed at one pound per acre.

and pigweed.

A spray containing various concentrations of the active Table V illustrates the herbicidal activity of the compounds when applied to crab grass, wild oats, buckwheat Table V Phytotoxicity Rating Conc., Active Ingredient Percent Crab Wild Buck- Pig- Grass Oats wheat weed p-Chlorophenyl 4-morpholinecarbothionate 0.2 4 2,4-dichlorophenyl e-morpholinecarbothionate 0. 5 3 4 1 p-Brgmophenyl 4morpholinecarbothiona P p-Ghtlorophenyl l-pyrrolidinecarbothioha a p-Chlorophenyl l-hcxamethyleniminecarbothionate Still further examples of the toxicants are p-chloro oingredient shown in Table IV was applied to the foliage of been plants, to the foliage of a mixture of grasses and finally to the foliage of a mixture of broadleaved plants. The mixture is indicated in the table as Broadleaf. A rating of 0 indicates no phytotoxicity, 1 slight, 2 moderate, 3 severe phytotoxicity, 4 plants dead and B defoliation.

tolyl-4-rn0rpholinecarbothionate, o-ch1or0-p-to1yl-4 morpholinecarbothionate, and 2-bromo-4-tertiary butylphenyl- 4-(2,6-dimethy1)morpholinecarbothionate. The presence of alkyl groups tends to alter the physical properties by lowering the melting point. For example, the last com- 1 25% defoliation. a 51-75% defoliation.

9 pound mentioned which was prepared by the process of Example 8, was an oil. Analysis gave 8.3% sulfur which is the same as the calculated value.

Table VI illustrates the pre-emergent herbicidal use of halophenyl carbothionates and demonstrates the necessity for substitution in the phenyl nucleus. The active ingredients were applied at a dosage of 25 pounds per acre to freshly seeded plots and phytotoxicity observed and recorded 14 days later in the manner previously described.

Table VI Active Ingredient Results Observed 2 brorno-4-tert.-butylpheny1 4-(2,6-dimethyl)morpholineearbothionate.

o-Chlorophenyl 4morpholinecarbothionate.

(mustard) Phenyl--morpholinecarbothionate. 2,4-diehloropheny1 4-(2,6dimethyl) Severe phytotoxicity to crab grass; moderate phytotoxicity to radish (mustard), sugar-beet barnyard grass, pigweed, tomato and sorghum.

Severe phytotoxicity to wild oats, sugar-beet, barnyard grass, crab grass, pigweed and wild buckwheat; moderate phytotoxicity to radish N phytotoxicity to any plants tested. Severe phytotoxicity to crab grass; moderate morpholinecarbothionate. phytotoxicity to barnyard grass. p-Chlorophenyl 4-(2,6-di.methyl Severe phytotoxicity to barnyard grass; moderate morpholinecarbothionatc. phytotoxieity to wild oats, rye grass and crab 2,4,6-trichlor0phenyl l-pyrrolidinegrass. Severe phytotoxicity to rye grass, and barnyard carbothionate. grass; moderate phytotoxicity to wild oats,

pigweed and sorghum. 2,4'dichloropl1eny1 l-piperidineearbo- Severe phytotoxicity to crab grass, wild oats,

thionate. rye grass, barnyard grass and sorghum. 2,4-dichlorophenyl dipropylthiono- No phytotoxicity to any plants tested.

carbamate.

In general, the new compounds may be represented by where R is piperidino, pyrrolidino, morpholino, 2- or 3- methylmorpholino, 2- or 3-ethylmorpholino, dimethylmorpholino, 2-, 3- or 4-methylpiperidino, dimethylpiperidino, as for example 2,3-, 2,4- or 2,6-dimethylpiperidino, ethylmethylpiperidiuo, as for example 5-ethyl-2-methylpiperidino, 5-ethyl-3-methylpiperidino, Z-ethyl-S-methylpiperidino, Z-ethyl 6 methylpiperidino, trimethylpiperidino, as for example 2,4,6-trimethylpiperidino, hexarnethylenimino and N-methylpiperazino and R is halophenyl as described above, alkoxyphenyl containing 1-4 carbon atoms inclusive in the alkoxy radical, 3,4-dimethoxyphenyl, 3,4 methylenedioxyphenyl, mononitrophenyl, methylphenyl providing that when p-substituted R is morpholino, dimethylmorpholino or pyrrolidino, and when o-substituted R is dimethylmorpholino, pyrrolidino or piperidino and alkylphenyl containing more than one but less than five carbon atoms in the alkyl radical providing R is pyrrolidino, piperidino or dimethylmorpholino.

The sub-class in which R is pyrrolidino may be represented by the formula S GE -CH where R represents phenyl substituted by lower alkyl, nitro or lower alkoxy radicals. Examples of R comprise substituted phenyl radicals in which the substituents are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, nitro, methoxy, ethoxy, propoxy, isopropoxy, butoxy and isobutoxy, as for example p-ethylphenyl, p-propylphenyl, o-ethylphenyl, m-ethylphenyl, 3,4-dimethoxyphenyl, 3,4- methylenedioxyphenyl, p-nitrophenyl, o-methylphenyl, pethoxyphenyl and o-ethoxyphenyl. Although other methods of synthesis are applicable, these compounds are readily obtained by condensing the appropriate alkali metal phenate with a pyrrolidinyl carbonyl halide.

EXAMPLE 18 To a stirred solution containing 24.4 grams (0.2 mole) of p-ethylphenol and 32.0 grams (0.2 mole) of sodium hydroxide was added in one portion at 25 C.

dinecarbothionate was obtained in 93.6% yield as an amber oil. Analysis gave 5.9% nitrogen and 13.5% sulfur as compared to 6.0% nitrogen and 13.6% sulfur calculated for C13H17NOS.

EXAMPLE 19 To a stirred solution containing 21.6 grams (0.2 mole) of p-cresol and 32.0 grams (0.2 mole) of 25% sodium hydroxide was added in one portion at 20 C. 29.9 grams (0.2 mole) of l-pyrrolidinethiocarbonyl chloride, causing a temperature rise to 45-50 C. The product was stirred for 5 hours without heating or cooling and then 250 ml. of cold water added. The reaction mixture was stirred for 15 minutes longer and then extracted with 250 ml. of ether. The ether solution was washed with water, dried over sodium sulfate and the solvent removed by distillation at a maximum temperature of 100 C. at 14 mm. pressure. The p-methylphenyl l-pyrrolidinecarbothionate was obtained in 97.2% yield as an amber oil. Analysis gave 6.2% nitrogen and 15.3% sulfur as compared to 6.3% nitrogen and 15.0% sulfur calculated for C H NOS.

EXAMPL'E 20 In the procedure of Example 19, 21.6 grams 0.2 mole) of m-cresol was substituted for the p-cresol. The m-methylphenyl l-pyrrolidinecarbot'hionate was obtained in 94.8% yield as an amber oil. Analysis gave 5.7% nitrogen as compared to 6.3% calculated for C H NOS.

EXAMPLE 21 In the procedure of Example 19 21.6 grams (0.2 mole) of o-cresol was substituted for the p-cresol. The o-methylphenyl l-pyrrolidinecarbothionate was obtained in 94.6% yield as an amber oil. Analysis gave 6.1% nitrogen and 15.3% sulfur as compared to 6.3% nitrogen and 14.5% sulfur calculated for C H NOS.

EXAMPLE 22 A solution was prepared by admixing 27.8 grams (0.2 mole) of p-nitrophenol, 32.0 grams (0.2 mole) of 25% sodium hydroxide in 50 ml. of water and ml. of acetone. To the solution so prepared at room temperature was'added in one portion 29.9 grams (0.2 mole) of l-pyrrolidinethiocarbonyl chloride in 80 ml. of acetone. An exothermic reaction began immediately. The reaction mixture was stirred for 5 hours and then 250 ml.

11: of water added. The solid product which precipitated was removed by filtration, washed with water and air dried. The p-nitrophenyl l-pyrrolidinecarbothionate was obtained in 87.2% yield as an amber solid, M.P. 156- 157 C. after recrystallization from ethyl acetate. Analysis gave 10.3% nitrogen and 13.0% sulfur as compared to 11.1% nitrogen and 12.7% sulfur calculated for C H N O S.

EXAMPLE 23 A solution was prepared by admixing 31 grams (0.25 mole) of p-methoxyphenol and 40 grams (0.25 mole) of 25% sodium hydroxide. To the solution so prepared there was added in one portion 37.4 grams (0.25 mole) of l-pyrrolidinethiocarbonyl chloride slurried in 80 ml. of acetone. The exothermic reaction caused the temperature to rise to 4050 C. The reaction mixture was stirred for hours without heating or cooling, then 250 ml. of water added. The oil was extracted with 250 ml. of ethyl ether, the ether solution washed with water and dried over sodium sulfate. Removing the ether by distilling in vacuo (95100 C./14 mm. Hg) left as the residue the desired p-methoxyphenyl l-pyrrolidinecarbothionate. It was an amber oil obtained in yield of 87.7%. It contained 5.7% nitrogen and 14.2% sulfur as compared to 5.9% nitrogen and 13.5% sulfur calculated for C H NO S.

EXAMPLE 24 Substituting m-methoxyphenol for p-methoxyphenol in the procedure of Example 23 resulted in a 92.6% yield of m-methoxyphenyl 1-pyrrolidinecarbothionate. It was an amber oil which contained 5.9% nitrogen and 13.8% sulfur.

The lower alkyl-, nitroand lower alkoxyphenyl lpyrrolidinecarbothionates also possess valuable biological activity. They are particularly useful for controlling vegetation by pre-emergent application to the soil medium. Some of these compounds are toxic to fungi. Amounts to be used for destroying vegetation and manner of formulation are similar to those described previously.

Table VII illustrates the pre-emergent herbicidal activity of typical aryl pyrrolidinecarbothionates. The ester was emulsified in water and the emulsion applied as a spray. In this manner, the active ingredient at a dosage of 25 pounds per acre was applied to the soil of seeded plots before the grass or other plants emerged. About fourteen days after application of the toxicants results were observed and recorded in the manner previously described. The following phytotoxicity ratings were observed:

Table VII The lower alkyl-, nitroand lower alkoxyphenyl morpholinecarbothionates include phytotoxic substances but exhibit greater structural specificity than the corresponding pyrrolidine compounds. This sub-group possesses the formula where R represents phenyl substituted by lower alkyl, nitro or lower alkoxy radicals and R represents morpholino or lower .alkyl substituted morpholino, as for example 2,6-dimethylmorpholino. Examples of R comprise phenyl substituted by methyl in the por o-positions, ethyl, propyl, isopropyl, butyl and isobutyl with the proviso that when the substituent in R is lower alkyl containing more than one carbon atom R is 2,6-dimethylmorpholino, nitro, methoxy, ethoxy, propoxy, isopropoxy, butoxy and isobutoxy radicals as for example 3,4-dimethoxyphenyl, 3,4-rnethylenedioxyphenyl, p-ethoxyphenyl and o-nitrophenyl. All of the examples illustrated herein are phytotoxic but are not necessarily equivalent.

EXAMPLE 25 To a stirred solution containing 24.4 grams (0.2 mole) of p-ethylphenol and 32.0 grams (0.2 mole) of 25 sodium hydroxide was added in one portion at 25 C. 38.7 grams (0.2 mole) of 4-(2,6-dimethyl)morpholinethiocarbonyl chloride in ml. of acetone. The exothermic reaction caused a temperature rise to 45 C. and was kept there by cooling. When the temperature started to drop, the ice-bath was removed, the product stirred for an additional 5 hours without heating or cooling and then 250 ml. of water added. The solution was extracted with 250 ml. of ether, the ether extract washed with Water and dried over sodium sulfate. The solvent was removed by distillation in vacuo at C. (approximately 14 mm. Hg). The p-ethylphenyl 4-(2,6-dimethyl)morpholinecarbothionate was obtained in 91.2% yield as an amber oil. Analysis gave 4.8% nitrogen and 11.5% sulfur as compared to 5.0% nitrogen and 11.5 sulfur calculated for C H NO S.

EXAMPLE 26 To a stirred solution containing 21.6 grams (0.2 mole) of p-cresol and 32.0 grams (0.2 mole) of 25% sodium hydroxide was added in one portion at 20 C. 38.7 grams (0.2 mole) of 4-(2,6-dimethyl)morpholinethiocarbonyl chloride in 80 m1. of acetone, causing a temperature rise to 45-50 C. The product was stirred for 5 hours without heating or cooling and then 250 ml. of water added.

Active Ingredient Results Observed p-Ethylphenyl l-pyrrolidincearbothionate.

p-Methylphenyl l-pyrrolidincearbothionate.

m-Methylphenyl l-pyrrolidinecarbothionatc.

o-Methylphcnyl l-pyrrolidinccarbothionatc.

p Nitr0pheny1 l-pyrrolidincearbothionate.

p-Methoxyphenyl l-pyrrolidinecarbothionatc.

m-Methoxyphenyl l-pyrrolidiuecarbothionate.

Severe phytotoxicity to brome-cheat grass, rye grass, sugar-beet, barnyard grass, pigweed, tomato and sorghum; moderate phytotoxicity to wild oats and wild buckwheat.

Severe phytotoxieity to wild oats, brome-cheat grass, rye grass, mustard family, sugar-beet, barnyard grass, crab grass, pigweed, soybean, wild buckwheat. tomato and sorghum.

Severe phytotoxicity to brome-cheat grass, rye grass, suganbcet, barnyard grass, crab grass, pigweed, wild buckwheat and tomato; moderate phytotoxicity to mustard family and sorghum.

Severe phytotoxicity to sugar-beet and pigwced; moderate phytotoxicity to crab grass, wild buckwheat and tomato.

Severe phytotoxicity to rye grass, sugar-beet, barnyard grass, crab grass and pigweed; moderate phytotoxicity to sorghum.

Severe phytotoxieity to wild oats, bromeeheat grass, rye grass, mustard family, sugar-beet. barnyard grass, crab grass, pigweed, wild buckwheat, tomato and sorghum.

Severe phytotoxicity to rye grass, barnyard grass, crab grass, pigweed and wild buckwheat; moderate phytotoxieity to wild oats, sugar-beet and sorghum.

EXAMPLE 27 A solution was prepared by admixing 27.8 grams (0.2 mole) of p-nitrophenol, 32.0 grams (0.2 mole) of 25% sodium hydroxide in 50 ml. of water and 80 ml. of acetone.

14 The toxicants may be applied in spray form. Amounts within the range of 1 to 60 pounds per acre will be adequate-for most purposes.

'Table- D( illustrates typical pre-emergent herbicidal activity. The ester was emulsified in water and the emulsion applied as a spray. In this manner, the active ingredient at a dosage of 'pounds per acre was applied to the ground of seeded plots before the grass or other plants emerged; About fourteen days after the application of the toxicants resultswere observed ahd recorded. The number of seeds emergin'g'wa's converted to weighted herbicidal ratings based-on average percent" germination of any particular seed lot times'an -injury'fact'or in the manner previously described. The followin'gphytotoxicity ratings were ob- To the solution so prepared at room tempera- 15 servedz' T able IX Active Ingredient Results Observed p-Ethylphenyl 4-(2,6-d1methyl)- morpholinecarbothionate.

p-Methylphenyl 4-morpholmecarbothionate.

p-Nltrophenyl 4-morpholinecarbothionate'.

p-Methoxyphenyl a-morpholinecab bothionate.

p-Methyl'phenyl 4 (2,6'-dim'eth'yl) -mo'rphollnecarbothionate. V I m-Methylphenyl 4-(2,6-dimethyl) -morpholinecarbothionate o-Methylphenyl 4 (2,6-dimethyl)-morpholinecarbothlonate. m-Methylphenyl 4-morpholinecarbothiona p A 7 m-Methoxyphenyl 4-morpholinecarbothionate. v H I V p Nitr0phenyl 4-(2,6-dimethyl)-morpholinecarbothionate.

Phenyl 4-rnorpholinecarbodithioate;1;

' Severe phytotoxiciy to wild oats, rye grass'and soybean.

Severe phytotoxicity to rye grass, sugar-beet,

barnyard grass, crab grass, pigweed, wild buckwheat and sorghum.

Severe phytotoxieity to morning glory, sugar-beet, pi'g'w'e'ed and tomato; moderate phytotoxicity to radish-mustard.

Severe phytotoxicity to rye grass, sugar-beet, barnyard grass, crab grass and pigwe ed; moderate phytotoxicity to brome-cheat'grass, wild buckwheat and sorghum.

Severe phytoto'xlcity' to" pi'g'weed; moderate phytotoxicity t0 barnyard grass.

Severe phytot'oxicity to sugar-beet, pigw'eed and soybean. M Severe phytotoxicity to pigweed and sorghum; moderate phytotoxieity to crab grass.

Severe phytotoxicity to pigweed;

phytotoxicity to sugar-beet. Severe phytotoxicity to pigweed and sorghum;

moderate Severe phy'totoxicity to sugar-beet; moderate phytotoxicity to soybean. No phytotoxicity to anyplants tested.

Methylphenyl i-morpholinecarbodithioate.

No phytotoxicity to any plants tested.

ture was added in one portion withstirring 33.1 grams (0.2 mole) of 4-morpholinethiocarbonyl chloride in 80 ml. of acetone. The exothermic reaction was stirred for 5 hours and then 250 ml. of water added. The water solution was filtered, the solid washed with water and air dried. The p-nitrophenyl 4-morpholinecarbothionate was obtained in 84.6% yield as a tan solid. After recrystallization from chloroform/heptane it' melted at 184-186 C. Analysis gave 9.7% nitrogen and 12.2% sulfur as compared to 10.4% nitrogen'and 12.0%' sulfur calculated for C11H12N2O4S- The physical properties of other typical examples prepared in similar manner are summarized below:

It will be noted that one oxygenato'minth'e acid radicalis' necessaryfor phytotox'icity.

Lower alkyl-', nitro-and lower alkoxyph'enylpiperidinecarboth'ionate's maybe represented by the formula where R represents phenyl substituted by lower alkyl, nitro or lower alkoxy radicals and R represents a six-membered h'eterocyclic hydrocarbon amino radical. Examples of R' comprise substituted phenyl radicals in which the substituents' are methyl, ethyl, propyl, isopropyl, butyl,

Table VIII Analysis, percent Example Yield,

No. Compound percent Physical Appearance Calcd. Found pdvlethylphenyl 4-morpho- 86. 5 Amber oil 5. 9 5. 6. linecrabothionate. 13. 5' 12. 7 m-Meth'ylphenyl 4-morpho- 92. 6 5. 9' 5. 6 linecarbothionate. 13. 5 13. 1 m-Methylphenyl 4'(2,6- 90. 5 5. 3' 5. 1 dimethyD-morpholiue- 12. 1 11. 8 carbothionate. v o-Methylphenyl 4-(2,6-di- 90.5 5. 3 5.0 methyD-morpholinecarbo- 12. 1 11. 4 thionate. p-Nrtrophenyl 4-(2,6-d1- 84. 3 Pale yellow solid, 9. 4' 9.0 methyD-morpholinecarbo- M.P. 1241-126 C. 10.8 11. 5 thionate. 33 p-Methoxyphonyl 4-1nor- 94. 0 Tan solid M.P. 93- 5. 5 5. 5 pholinecarbothionate. 94 C. 12. 7 I 13.0 34.; m-Methoxyphenyl -mor- 80. 7 Amber oll-. q 5. 5 5.0 pholinecarbothionate; 12; 7 11. 7

The'lower alkyl-, nitroand lower alkoxyphen'yl morpholinecarbothionates herein described have theproperty of destroying vegetation in pre-emergent application. Pigweed is especially sensitive to the methylphenyl and methoxyphenyl esters, which esters are also toxic to fungi.

isobutyl, nitro, methoxy, ethoxy, propoxy, isopropoxy, butoxy and isobutoxy, as for example p-ethylphenyl, 3,4-dimethoxyphenyl, 3,4 methylenedioxyphenyl, p-nitrophenyl and o-methylphenyl. Examples ofR-comprise piperidino, 5-ethyl-2-methylpiperidino and Z-methylpipridino.

1. EXAMPLE 35 To a stirred solution of 24.4 grams (0.2 mole) of pethylphenol, in 32 grams (0.2 mole) of 25% sodium hy- 16 carbothionates are in general innocuous to foliage, the products of Examples 37-40 are useful pre-emergence herbicides. They destroy germinating pigweed seedlings at a dosage of 25 pounds per acre. On the other hand,

droxide was added in one portion 32.7 grams (0.2 mole) 5 of l-piperidinethioearbonyl chloride in 80 ml. of acetone. gi g g f gigggg 2385522 22 ggz ggi efiect 61th gr An exotherfrilc reacuon i m but i tefnperahure was It is intended to cover all changes and modifications kept from nsmg above 45 by coolmg an Ice bath of the examples of the invention herein chosen for pur- When the temperatulie staried to 9 the 165 bath wa poses of disclosure which do not constitute departures moved and the react on mixture stirred for an additional 10 from the spirit and Scope of the invention.

5 hours wlthout heating or coohng. After adding 250 m1. What is claimed is:

of water the reaction mixture was extractedwith ethyl A thionocarbamate of the formula Selected from ether. The ether extracts were dried over sodlum sulfate the group consisting of;

and the solvent removed by distillation in vacuo (100 (3) S C./ 14 mm. of Hg). p-Ethylphenyl l-piperidinecarbothio- 15 &

nate was obtained in 87.2% yeild as an amber oil. It con R' o tained 5.2% nitrogen as compared to 5.7% calculated for where R is selected from a group consisting of piperi- C H NOS. dino, pyrrolidino, morpholino, Z-methylmorpholino,

The physical properties of other typical examples pre- 3-methylmorpholino, 2 ethylmorpholino, 3 ethylpared in similar manner are summarized below: 20 morpholino, 2,5-dimethylmorpholino, 3,5-dirnethyl- Table X Analysis, Percent Example Compound Yield, Physical Appearance N0. Percent Calcd. Found 36 m-Mcthylphenyl l-piperi- 87.3 Amber oil N 5.9 6.0 dineearbothionate. 13. 6 13. 6 37 o-Methylphenyl l-piperi- 86.3 do 5.9 5.8 dinecarbothionate. 13. 6 13. 0 38 p-Nitrophenyl l-piperi- 97.5 Tan solid M.P. 106- 10.5 9.6 dinecarbothionate. 107 from ethanol. 12.0 12. 5 39 p-Methoxyphenyl l-piperi- 94.0 Amber oil 5.6 5.4 dinecarbothionate. 12. 7 12. 8 i0 rn-Methoxyphenyl l-piperi- 95.5 .do 5.6 5.4

dineearbothionate.

The lower alkyl-, nitroand lower alkoxyphenyl piperimorpholino, methylpiperidino, 2,3-dimethylpiperidinecarbothionates also possess useful biological activity. 40 dino, 2,4-dimethylpiperidino, 2,6-dimethylpiperidino, The foregoing examples of this class are valuable for con 5-ethyl-Z-methylpiperidino, 5 ethyl-3-methylpiperitrolling cereal rusts or other fungus diseases. The presdino, 5-methyl-2-ethylpiperidino, 2-ethyl-5-methylence of the substituents in the phenyl ring supports the bipiperidino, 2 ethyl-6-methylpiperidino, 2,4,6 triological activity. methylpiperidino, hexamethylenimino, and N-meth- Typical of the effectiveness of the products of the ylpiperazino and R is selected from a group conpresent invention as fungicides is the action of the new sisting of monochlorophenyl, p-chloro-o-tolyl, 0- materials in protecting against the destructive action of chloro-p-tolyl, 2-bromo-4-butylphenyl, 2,4-dichlorothe organism Puccinia rubigo-vera tritici. In demonstratphenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2,3- ing this effectiveness a rust susceptible variety of wheat dichlorophenyl, monoalkoxyphenyl of 1-4 carbon (Seneca) was planted in small clay pots filled with soil. atoms, inclusive, in said alkoxy, 3,4-dimethoxy- About ten seeds were normally planted in each pot so to phenyl, 3,4-methylenedioxyphenyl, mononitroph m insure availability of five uniform plants for the test. yl, and m-methylphenyl;

The pots were held in a greenhouse at 75 F. and watered (b) 8 daily until the seedlings were six days old. Thereupon I J] the seedlings were sprayed with water by means of an RTO TR atomizer and bloom removed from the leaves by gentle 5 Where R is Selected from 3 gr p consisting of P P rubbing. Then rust spores were transferred to the leaves dino, PYffQlidillO, morpholino, z-methylmofpholino, and rubbed up and down the leaves. Four days after 3methylmorpholino, 2 ethylmorpholino, 3 ethylinoculation with rust spores, the plants were sprayed with morpholino, methylpiperidino, 2-3-dimethylpiperisolutions of the chemical under test, prepared in condino, 2,4-dimethylpiperidino, 2,6-dimethylpiperidino, centrations of from 1 to 5 parts chemical to 1000 parts S-ethyl-Z-methylpiperidino, 5 ethyl-3-methylpiperiof water which contained a small quantity (5 parts) of dino, S-methyl-2-ethylpiperidino, 2-ethyl-5-methylacetone if the chemical was not water soluble. A trace piperidino, 2 ethyl-6-methylpiperidino, 2,4,6 triof a suitable spreading or wetting agent preferably was methylpiperidino, hexamethylenimino, and N-methalso present. The plants were sprayed in duplicate tests ylpiperazino and R is selected from the group con using 10 cc. of the test solution per pot. After treatsisting of monobromophenyl and monofiuorophenyl; ment as described, the pots were held in the greenhouse (0) s for a week and examined and graded as to the number I g and size of pustules formed on the leaves. The products R O R f Examples 9 20 24 27 29 34, 3 5 36, 37 and 3 where R 1s selected from a group consisting of piperihereinbefore described, taken as typical of the products dino, Pyrfolldino, methylpipefidino, y herein disclosed, in concentrations between 1 to 5 parts P P? 3 P P fi- Y P per 1000, that is of from 0.1 to 0.5% by weight, showed P P Y y p p y good results as eradicants of foliage wheat rust. There YIPIPeYIdIHO, Y y p p y was also from no to very slight injury of the leaves. methylpiperidino, 2,6 methylpiperidino, 2,4,6 tri- Although the alkyl-, nitroand alkoxyphenyl piperidinemethylpiperidino, hexamethylenimino, and N-meth- 17 ylpiperazino and R is selected from a group consisting of 2,4-dibromophenyl and 2,4-difluorophenyl;

RO( R where R is pyrrolidino and R is selected from a group consisting of 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, and 2,4,6- trihalophenyl, the halogen being selected from a group consisting of chlorine, bromine, and fluorine;

R'OJZLR where R is selected from a group consisting of morpholino, 2,6-dimethylmorpholino, 3,5-dimethylmorpholino, and pyrrolidino and R is p-methylphenyl;

R-O! JR where R is selected from a group consisting of 2,6-dimethylmorpholino, 3,5-dimethylmorpholino, pyrrolidino, and piperidino and R is o-methylphenyl;

RO -R where R is selected from a group consisting of pyrrolidino, piperidino, 2,6-dimethylmorpholino, and 3,5-dimethylmorpholino and R is alkylphenyl of more than one but less than five carbon atoms in said alkyl. 2. A compound of the formula 01 i 5 f3 CIOCN\ (H2 i CHgGHz where X and Y represent chlorine and n represents an integer from zero to one inclusive.

4. p-Chlorophenyl 4-morpholinecarbothionate.

5. p-Bromophenyl 4-morpholinecarbothionate.

6. p-Bromophenyl l-pyrrolidinecarbothionate.

7. 2,4-dihalophenyl l-pyrrolidinecarbothionate.

8. p-Chlorophenyl l-pyrrolidinecarbothionate. 5 9. A thionocarbamate of the formula where R represents lower alkyl of l to 4 carbon atoms.

10. A thionocarbamate of the formula N02 s GET-CH2 \C HzCHg 11. A thionocarbamate of the formula R s CHE-CH2 CH- H,

where R represents lower alkyl of l to 4 carbon atoms.

/0H, GH -0H2 where R represents lower alkoXy of 1 to 4 carbon atoms.

15. p-Ethylphenyl l-piperidinecarbothionate.

References Cited by the Examiner UNITED STATES PATENTS 3/ 1941 Williams 260-239 6/1960 Goodhue 260-425 7/1951 Harman et al 260--455 NICHOLAS S. RIZZO, Primary Examiner.

WALTER A. MODANCE, Examiner. 

1. A THIONOCARBAMATE OF THE FORMULA SELECTED FROM THE GROUP CONSISTING OF:
 4. P-CHLOROPHENYL 4-MORPHOLINECARBOTHIONATE. 